Azo dyestuffs



Patented Apr. 2, 1940 UNITED STATES- PATENT OFFICE 2,195,784 I AZO DYESTUFFS Max Schmid, Riehen, near BaselQSW'itzrland,

assignor to the firm of Society of Chemical Industry in Basle, Basel, Switzerland 1 No Drawing. Application November 2,1936, Se:- rial .No. 108,902. In Switzerland'November 6,

This invention relates to new dyestufis Ob tained from new intermediate products which are obtained themselves by converting by known 'methodsinto the corresponding hydrazine a compound of the general formula p or a hetero-cyclic ring such as and th e like, and R1 is they residue of an organic (1 =hydrogen or any substituent) acid, and condensing in known manner,"after saponifying the radical of the organic acid, if this is present, with a suitable keto-compound to producea pyrazolone capable of being coupled.

The new compounds, which correspond with the general formula in which a: has the meaning ascribed be it above,

R1 stands for hydrogen or a radical of an organic acid and Py represents the pyrazo-lone radical, canbe converted into I newv a'zo dyestuffs either by coupling them with diazo compounds or by saponifying any radical of an organic acid that may be present, then diazotizing and con-'- pling with coupling component'slcr by using both reactions together.

The new azo' dyestuffs are characterized by the presence of the atom grouping in which-Py and a: have the meaning ascribed to the fiber.

of the formula *lClairns, v(c1. 260-147) R1 l IH 1 I NH," 1

there maybe mentioned benzidine, diphenyline tolidine, dianisidine, diphen-etidine, thioaniline, 4 4-diamino-diphenyl ether, 4:4'-diaminostilbene, 4:4 diaminodibenzyls, 4:4 or 3:3 -diaminodiphenylmethane, 4:4 diaminodiphenylamines, 4:4'- or 4:3 or 3:4- or '3:3-diaminobenzoylaniline, 4:4'-diamino-diphenyl urea, the

condensation product from 2 or 3 mol metaphenylenediamine or paraphenylenediamine and 1 mol cyanuric chloride or thecondensation product from 1 mol cyanuric chloride, 1 mol aniline and 2 mol para-phenylenediamine or metasphenylenediamine or similarly constructed condensation products in which the cyanuric ring is replaced by similar. six-membered hetero rings containing carbon and nitrogen, such as those of the pyrimidine, the quinazoline, the phthalazine and the like, which correspond toproducts in which the linkage :c can be formulated for example as Compounds of the general formula CH! I n NH NON-o C-N- NHa lHr-O I111 1 06cm are therefore, for example, monoformylbenzidine, monoacetylbenzidine, monobenzoylbenzidine, 4- or 3-acetylamino- 1-(4 or 3'-amino) benzoylaminobenzene, 4 amino- 1 (4 or 3' acetylamino) benzoylaminobenzene 3 sulfonic acid, products obtained by monobenzoylation or monoacetylation from the reduced condensation products from 1 mol urea chloride or isocyanate from paraor meta-nitraniline and 1 mol 1:4-diaminobenzene-3-sulfonic acid, such as NEH-O l EIJIII NHLo 0.0m

H o H SOaH the ternary condensation products from 1 mol 1:4- or 1:3-diaminobenzene-3- or -sulfonic acid, 1 mol monoacetyl-paraor meta-phenylenediamine and 1 mol of a primary or secondary amine and 1 mol cyanuric chloride such as A NHz-ON-(fl) \o-rr-Qnaooom N N HOaS 3 HN-OOCH: and the like.

I NH

Such pyrazolones are, for example, the following:

coon

and so on, as indicated in the fifth paragraph of this specification.

Among the diazo-com'pounds which may be coupled with such products there must first be named the simple diazo-compounds, such as diazobenzene, diazonaphthalene, diazotoluene, diazoanisole, diazophenetole, diazotized aminoazobenzene or the like and sulfonic acids of them. Of particular interest are, however, the diazocompounds which have in orthoor peri-position to the diazo-group a hydroxyl group or a carboxyl group. Such diazo-compounds are, for example, those of ortho-aminophenols, ortho-aminonaphthols and their sulfonic acids, the diazocompounds of 1:8-aminonaphthol sulfonic acids, also of ortho-aminocarboxylic acids, for instance anthranilic acid. With the aid of such compounds dyestuffs are obtained which can be converted into valuable metal compounds on the fiber or in substance by means of agents which yield metal, for instance copper salts, chromium salts or hydroxides of these metals.

Of these-dyestuffs those are of especial value which are obtained by treating with copper on the fiber or in substance the azo dyestuffs which are themselves obtained by coupling the intermediate product of the general formula with a diazotized ortho-amino-carboxylic acid of the benzene series. These new dyestuffs are therefore the copper compounds of dyestufis of the general formula These new dyestuffs are yellow to brown-yellow powders soluble in water to a yellow solution and producing on cotton, whether dyed as such or produced on the fiber by subsequent treatment of the non-metallized azo dyestuff with an agent yielding copper, yellow tints which are characterized by their excellent fastness to light. They correspond to the copper compounds of the dyestuffs of the generalformula wherein R stands for an aromatic nucleus of the benzene series which is substituted in ortho position to the -N=N-'- group by a COOH group,

1/ stands for a member of the group consisting of H, methyl, phenyl, 0001-1 and COO alkyl, :1: stands for a member of the group of linkages and a heterocyclic six membered ring consisting of at least 3 and not exceeding 4 carbon atoms,

group does not belong to the heterocyclic radical,

and R1 stands for the radical of a polyvalent organic acid.

The dyestuffs obtained by the invention may, as already stated, especially be used for dyeing vegetable fibers. They may also be'u'sed with i a like result for dyeing regenerated'cellulosc, for

instance, viscose or copper silk. Should the new dyestuffs contain suitable substituents they may be diazotized on the fiber and developed by further coupling components or by treatment with a diazo compound. When the dyestuffs have been made with the aid of o-rtho-amino-phenols, ortho-aminocarboxylic acids or their esters or ethers, or when they contain the salicylic acid grouping or other lake-forming groups of atoms they are capable of conversion into metal compounds. Suitable metals coming into question besides the copper and chromium already mentioned are nickel, cobalt, iron, zinc or the like. The metal compounds may be obtained either on the fiber or in' substance.

The new azo dyestuffs obtain-able according to the present process correspond to. the general formula in which R stands for a nucleus selected from the group consisting of aromatic nuclei of the benzene and naphthalene series, 1 stands for a member of the group consisting of H, methyl, phenyl, COOH and C00- alkyl, :c stands for a member of the group of linkages consisting of a diphenyl linkage, O-, S-, CH=CH, CH2CH2-, 'CI-I2--, -NH,

and a heterooyolic six-membered ring consisting of at least 3 and not exceeding 4 carbon atoms, and at least 2 and not exceeding 3 nitrogen atoms, not more than 2 nitrogen atoms standing adjacent to each other, which ring further contains at least twice and not more than three times the atom grouping I I H N wherein the ]T' group does not belong to the heterocyclic radical, and 2 stands for a member of a groupoi substituents linked to the benzene nucleus by N-atoms and consisting of a member of the group consisting of N=N-R1, R1 standing for an aromatic nucleus from the group consisting of aromatic nuclei of the benzene and naphthalene series, and

R2 standing for the radical of an organic acid, which dyestufis are yellowto brown and black powders dissolving in water to yellow to orange, to brown, to blackish and to green solutions, and dyeing the fiber similar tints of good fastness.

The following examples illustrate the invention, the parts being by weight:

Example 1 22.6 parts of finely ground monoacetylbenzidine are stirred in 50 parts of water and someice with 30 parts of hydrochloric acid of specific gravity 1.15. Into this mixture there is dropped slowly at 0l0 C. a solution of '7 parts of sodium nitrite in about parts of water and when the-addition of this nitrite is complete the whole is stirred for about 1 hour and then filtered.

The filtered diazo solution is run at 0-5" .C. while stirring well into an externally cooled mixture of 100 parts of stannous chloride of about 63 per cent. strength and. 50 parts of hydrochloric acid of specific gravity 1.15.

' The hydrazine thus formed is sparingly soluble. After stirring for about 12 hours the mixture is filtered and the solid washed with dilute hydrochloric acid and then With water. By stirring, this solid matter, if desired after separation of the tin, with dilute alkali the free hydrazine of v the formula NHPNEFQQNH. o 0 CE:

is obtained. From alcohol it crystallizes in the form of bright yellow needles of melting point 227 C. Alternatively the filtered diazo solution is run whilst stirring into a mixture of 632 parts of bisulfite liquor of 40 per cent. strength, 30 parts of sodium carbonate and 50 parts of caustic soda solution of 36 B. Stirring is continued during the night and the product is salted out and filtered. The filter cake is stirred into 2000 parts of water and after addition of 60 parts of acetic acid the whole is heated to boiling. There are then added gradually about 60 parts of zinc dust and boiling is continued until the mass is decolorized. After filtering hot the hydrazine sulfonic acid of the formula is salted out from the cool filtrate.

The hydrazine sulfonic acid can be converted into the hydrochloride of the hydrazine base by treatment with hydrochloric acid.

In like manner products can be prepared from the parent materials indicated in the th paragraph of this specification.

Example 2 The hydrazine hydrochloride of the formula HCl-NHz-NEE-QO-NH. o 0.011:

obtainable as described in paragraphs 1-3 of Example 1 is boiled together with 590 parts of water and 100 parts of hydrochloric acid of specific gravity of 1.15 for about 2-3 hours, whereby the hydrochloride is dissolved. If desired the solution may be treated with sulfurated hydrogen to remove tin, if necessary, filtered and cooled. The large part of the hydrochloride separates and a further quantity may be salted out from the mother liquor or the latter may be treated with alkali to recover the free base.

This base may be recrystallized from alcohol when it forms white crystals of melting point 179 C. which become brown on exposure to air and correspond with the formula The corresponding product from monoacetylortho, ortho-tolidine crystallizes from alcohol in white laminae of melting point 184 C. It has the formula CH3 CH3 Example 3 24.1 parts of the hydrazine of Example 1 are dissolved in about 200 parts of alcohol mixed with some glacial acetic acid. There are then added 14 parts of ethylaceto-acetate and the mixture is boiled for about 1 hour. After cooling there are added to the mixture 20 parts of caustic soda solution of 36 B. and the mixture is stirred for 24 hours. By heating the larger part of the alcohol is expelled while water is substituted, the whole is filtered and pyrazolone precipitated by adding acid. It corresponds with the formula The condensation may also start from the hydrazine hydrochloride and be conducted in aqueous medium. In similar manner products are obtained from the other hydrazines indicated in Example 1. Instead of ethylaceto-acetate any other fi-ketocarboxylic acid ester, for instance ethyl benzoyl acetate, terephthaloyl di-acetic ester, ethyl oxal-acetate or the sodium compounds thereof may be used.

Example 4 27.2 parts of the hydrazine hydrochloride of Example 2 are suspended in hot water. Condensation follows with 14 parts of ethylacetoacetate at about 60 C. with gradual neutralization of the acid liberated in the condensation. When the condensation is complete the whole is cooled, made alkaline to phenolphthalein by means of caustic alkali, stirred for 12 hours, heated until everything has been dissolved and finally the pyrazolone precipitated by neutralization. It corresponds with the formula This new product is a white powder of melting point 194 C., soluble in dilute caustic soda solution and. dilute mineral acid.

Example 5 30.? parts of l-phenyl-(4-phenyl-4"-acetylamino) -3-methyl-5-pyrazolone of the formula r C=N /N NH.CO.CH: CHT-CO obtainable as described in Example 3 are dissolved in about 500 parts of water containing parts of caustic soda solution of 36 Be. and parts of calcined sodium carbonate.

The filtered solution is mixed gradually with the diazo-compound from 17.5 parts of sulfanilic acid. When coupling is complete the whole is heated and the dyestuii salted out and isolated as usual. It is an orange-yellow powder and dyes cotton yellow tints. The dyestuff corresponds with the formula By substituting for the diazotized sulfanilic acid of this example another diazo-component further direct dyeing dyestuffs may be obtained. By using non-sulfonated diazo-compounds valuable pigments are formed while when an orthohydroxyor ortho-carboxy-diazo-compound is used dyestufis which can be metallized are produced.

Thus, for example the dyestuff from diazotized sulfoanthranilic acid and 1-phenyl-(4 -phenyl- 4' '-acetylamino) -3-methyl5-pyrazolone produces yellow tints on viscose artificial silk or natural silk which become fast to light when aftertreated with copper. The copper compound of the dyestufi dyes itself cotton yellow tints.

Further products dyeing yellow to brown-red tints are obtained by replacement of the sulfoanthranilic acid by ortho-aminophenol-sulfonic acids of the benzene or naphthalene series, such as sulfo-amino-salicylic acid, -chloro-il-aminophenol-S-sulfonic acid, 4-nitro-2-aminophenol- G-sulfonic acid, l-aminc-Z-hydroxynaphthalene- 4-sulfonic acid, Z-amino-l-hydroxynaphthalene- 4:8-disulfonic acid, etc., and conversion of the new azo-dyestufis into their copper compounds.

Similar dyestuffs can be obtained by replacing the l-phenyl-(4-phenyl--l"acetylamino) 3-' methyl-5-pyrazolonc by the corresponding 1- phenyl-(4'-phenyl4"-acetylamino) 5 pyrazolone-3-carboxylic acid. Further, the -i-acctylamino group can be replaced by an amino group which is substituted by another organic acid radical. Such acid radicals may be radicals of mono-carboxylic acids, such as propionic acid, butyric acid, capric acid, benzoic acid, cinnamic maleic acid, phthalic acids and sulfo-phthalic acid, two or also only one carboxylic acid group i being amidated. Finally, the 4-NH2-7g'rou'p may be substituted by such acid radicalswhich are not carboxylic acid radicals. As examples of these there may be cited the radicals of the paratoluene-sulfonic acids or the cyanuric acid.

The introduction of such radicals into the dyestuffs of the general formula may also take place according to known methods. Such dyestuffs are for example the dyestuffs or the copper complexes ofj'the dyestuffs of the following formulas:

O P 1 2 2 3 3 4 g eny SO56 mmm amw m B aw mmwm wwm s w m dm .wxem H i m on M E N 0 mu wm mwwxflw r w 8 a O O C mmm r Cl C S| h 1 rrt h dfl s c D N SpXe m u fia n oo h c N wmm nm n O fiaaw m w i l N H 0 N/\C..H0 M N pi msnm N H mh mm m m SNHHDO 0 W10 .Kc OS W .llS h fln e e ntth m e h eft 8 b {\0 lyoeh t f J dfim o n: nm w mee m i t m H am mmnmma am I. 3 ea H mmn nmaa N G N N cl wh a H fi z och d CNN .1 mmawmam m m N IH H ccfibcyw mmaum JUIO m N NIH m um mh fit nm mm e W mm m. D 8 n5 mm |fi m N N mM at cc memm m a a l t a iilll A N as mm m H N wfi C C H e cl 0 H N Sm vmp 0 M wa N m 0 l dy m n. aw mm mam R St m mm mm m m H .wm mm I s m m W H wm 0 1 M m w w m another linkage cited in the introduction. Comyields on cotton yellow tints. The complex coppare also the last paragraph of Example 1 and per, chromium, nickel and cobalt compounds of the last paragraph of Example 3. Examples of this dyestufi yield also yellow tints on cotton. such dyestufis are: The iron compound yields brownish yellow tints.

These dyestuffs are above all valuable as metal The copper compound of the dyestuff of the compounds, and then particularly as copper formula.

is an orange-brown powder dyeing the fiber or ange-brown tints, and the dyestuif of the formula for the radical of' an amino-monoazo dyestuff, both radicals A'and B being united to the carbon lYThe metal compounds of the sulfonated azo dyestuffs Containing at least one am group and corresponding to the general formula in which R. stands for a nucleus selected from the glOlip consisting of aromatic nuclei of the benzene and, naphthalene series which are substituted infertile-position to the -N=N group by a lake-forming group consisting of a member of the group consisting of OH and 0001-1, 3 stands for a member of the group consisting of methyl, 'phenyl, COOl-I and CD0+ alkyl, a:

stands for a member of the group of linkages conand a heterocyclicsix-membered ring consisting of at least 3 and not exceeding 4 carbon atoms, and at least 2 and not exceeding 3 nitrogen atoms, not more than 2 nitrogen atoms standing adjacent to each other, which ring further contains atleast twice'and not more than three times the atom grouping I I N wherein the group does not belong to the heterocyclic radical, R1 stands for a radical wherein A stands for the radical of an aromatic,

-gmono-nuclear siX-membered amine and B stands atom of the triazine nucleus by the N-atom of their amino-groups, the groups \N--, zand III -R1 not being in ortho-position to one another, which dyestufis are yellow to brown and black powders dissolving in water to yellow to orange and to brown solutions, and dyeing the fiber similar tints of good fastness.

2. The copper compounds of the sulfonated azo dyestuffscontaining at least one azo group and corresponding to the general formula in which R stands for a nucleus selected from the group consisting of aromatic nuclei of the benzene and naphthalene series which are substituted in ortho-position to the --N=N- group by a lake-forming group consisting of a member of the group consisting of OH and COOH, 3/ stands for a member of' the group consisting of H, methyl, phenyl, COOH and C00- alkyl, It stands for a member of the group of linkages consisting of a diphenyl linkage, O, -S, -CH=CH, C I-I 2CH2--, CH2, --NI-I,

and a heterocyclic sixmembered ring consisting of at least 3 and not exceeding 4 carbon atoms, and at least 2 and not exceeding 3 nitrogen atoms, not more than 2 nitrogen atoms standing adjacent to each other, which ring further contains at, least twice and not more than three times the atom grouping wherein the group does not belong to the heterocyclic radical, R1 stands for a radical wherein A standsv for the radical of an aromatic,

mono-nuclear six-membered amine and B stands for the radical of an amio-monoazo dyestuff, both radicals A and B being united to the carbon atom of the triazine nucleus by the N-atom of their amino-groups, the groups not being in ortho-position to one another, which dyestuffs are yellow to brown and black powders dissolving in water to yellow to orange and to brown solutions, and dyeing the fiber similar tints of good fastness.

3. The copper compounds of the sulfonated azo dyestuffs containing at least two azo groups of the general formula wherein y stands for a member of the group consisting of H, methyl, phenyl, COOH and C00- alkyl, R stands for a nucleus selected from the '7 group consisting of aromatic nuclei of the benzene dyestufi, which dyestufis are soluble in water to yellow, orange and brown solutions, and dye the fiber similar tints, which can be after-treated with copper.

4. The copper compounds of the sulfonated azo dyestufis containing at least one azo group and corresponding to the general formula of H, methyl, phenyl, COOH and COO alkyl, 1'

stands for a member of the group of linkages consisting of a diphenyl linkage, -O-, S--, CH=CH--, CH2--CH2-, CH2, NH,

and a heterocyclic six-membered ring consisting of at least 3 and not exceeding 4 carbon atoms, and at least 2 and not exceeding 3 nitrogen atoms, not more than 2 nitrogen atoms standing adjacent to each other, which ring further contains at least twice and not more than three times the atom grouping l H N- wherein the group does not belong to the heterocyclic radical, the groups not being in ortho-position to one another, which dyestufis are yellow to brown-yellow powders dissolving in water to yellow solutions, and producing on cotton yellow tints characterized by their iastness, especially by their excellent fastness to light.

5. The copper compounds of the sulfonated azo dyestuffs containing at least one azo group and corresponding to the general formula wherein R stands for an aromatic nucleus of the benzene series which is substituted in ortho-position to the N=N- group by a COOH- group, and y stands for a member of the group consisting of H, methyl, phenyl, COOH and COOalkyl,

which dyestuffs are yellow to brown-yellow pow- 60 ders dissolving in water to yellow solutions, and

wherein R stands for an aromatic nucleus of the benzene series which is substituted in ortho-position to the --N=N-- group by a COOH group, y stands for a member of the group consisting producing on cotton yellow tints characterized by their fastness, especially by their excellent fastness to light.

6. The copper compounds of the sulfonated azo 75 dyestuffs containing at least one azo group and COO-alkyl, which dyestufis are yellow to browncorresponding to the general formula. yellow powders dissolving in water to yellow soluin which R stands for an aromatic nucleus of the benzene series which is substituted in ortho-position to the -N=N group by a, COOH group, and y stands for a member of the group consisting of H, methyl, phenyl, COO-H and acterized by their fastness, especially by their exceilent fa-stnessto. light.

7. The copper compound of the azo dyestufi of the formula IMZAX SCEMID.

tions, and producing on cotton yellow tints ohar- 

